Nitrate concentration Measurement in Cress Plant Using a Colorimetric Sensor based on Gold nanoparticles

Document Type : Research Paper

Authors

1 Soil Science Department, ' Faculty of Agricultur, University of Tehran, Iran

2 Soil Science Department,, ّFaculty of Agriculture, University of Tehran' Iran

3 Department of Nanotechnology, Agricultural Biotechnology Research Institute, Karaj, Iran

Abstract

Due to the necessity of regular and rapid evaluation of nitrate, the development of methods with the ability to detect this compound accuratly and simple is important. Nowadays, colorimetric methods have received much attention due to their ability to detect simple and visual. In this study, which was carried out in 2022 with cooperation of Tehran university and the Agricultural Biotechnology Research Institute, a colorimetric method based on etching of gold nanorods for qualitative and quantitative detection of nitrate was presented. the measurement of nitrate ions (after reduction of nitrate to nitrite by zinc powder) at room temperature is possible by changing the size of the plasmonic nanoparticles and subsequently generating measurable signals, including spectral and color changes. Under optimal conditions, a good linear relationship between nitrate concentration and colorimetric response in the range of 0.5 to 3.0 mM (R2=0.995) with a detection limit of 173.3 μM was found. Also, considering that vegetables, especially leafy vegetables, have a high potential in nitrate absorption, in this research cress plant was used as an indicator plant to investigate the efficiency of the sensor in determining the nitrate of leafy plants. Recovery values for nutrient solution and cress tissue samples was in the range of  94.4 to 101.9 and 93.4 to 98.5%, respectively, and relative standard deviation (RSD) for all samples was calculated below 2.1%. As a result, the presented method in this study provides the possibility of monitoring the actual level of nitrate in cress plant samples.

Keywords

Main Subjects


Nitrate concentration Measurement in Cress Plant Using a Colorimetric Sensor based on Gold nanoparticles

Extended Abstract

Introduction:

The presence of nitrate in environmental matrices, especially the water-soil-plant system, has raised concerns in the scientific community due to its negative effects on the environment and the health of living organisms. Due to the necessity of regular and rapid evaluation of nitrate, the development of methods with the ability to detect accurate and insitu of this compound is very important. In general, traditional and laboratory methods, despite their high sensitivity, are not very satisfactory due to problems such as time consuming, expensive, inability to measure quickly and the production of chemical waste. Today, colorimetric methods have received much attention due to their ability to detect visually and in situ. Accordingly, in this study, a colorimetric method based on etching of gold nanoparticles with rod shapes for qualitative and quantitative detection of nitrate was presented.

Materials and Methods:

This study was carried out in 2022 at the agricultural biotechnology research institute and the university of tehran, soil science department. Unlike other studies, in this method, instead of temperature, thiourea was used as a sulfur-containing compound to accelerate the etching process of gold nanoparticles. Thiourea accelerates the etching process by forming a complex with gold ions and thus reducing the oxidation potential of Au+ / Au. Therefore, the measurement of nitrite ions at room temperature is possible by changing the size of the plasmon nanoparticles and subsequently generating measurable signals, including spectral and color changes. In addition to nitrite, the developed method is able to determine nitrate indirectly (after reduction of nitrate to nitrite by zinc powder).

Results and Discussion:

Under optimal conditions, a good linear relationship between nitrate concentration and colorimetric response in the range of 0.5 to 3 mM (R2=0.995) with a detection limit of 173.3 μM was found. Also, considering that vegetables, especially leafy vegetables, have a high potential in nitrate absorption, in this research cress plant was used as an indicator plant to investigate the efficiency of the sensor in determining the nitrate of leafy plants. Recovery values for nutrient solution and cress tissue samples were in the range of 94.4 to 101.9 and 93.4 to 98.5%, respectively, and relative standard deviation (RSD) for all samples was calculated below 2.1%. These results show that the proposed measurement system will be able to accurate detection of nitrate content in real samples because a great similarity was observed between the nitrate concentration in the sample (initial concentration + spiked concentration) and the concentration obtained by the sensor.

Conclusion:

Evaluation of this sensor using samples of food solution and cress plant shows its ability to measure nitrate concentration with high accuracy and sensitivity in all tested samples. As a result, the method presented in this research makes it possible to measure and monitor the actual level of nitrate in environmental and food samples and can provide valuable data about the amount of these compound in complex matrices.

Ahluwalia, A., Gladwin, M., Coleman, G. D., Hord, N., Howard, G., Kim‐Shapiro, D. B., & Harman, J. L. (2016). Dietary nitrate and the epidemiology of cardiovascular disease: report from a National Heart, Lung, and Blood Institute Workshop. Journal of the American Heart Association, 5(7), e003402.
Alahi, M. E. E., & Mukhopadhyay, S. C. (2018). Detection methods of nitrate in water: A review. Sensors and Actuators A: Physical, 280, 210-221.‏
Bahadoran, Z., Mirmiran, P., Jeddi, S., Azizi, F., Ghasemi, A., & Hadaegh, F. (2016). Nitrate and nitrite content of vegetables, fruits, grains, legumes, dairy products, meats and processed meats. Journal of Food Composition and Analysis, 51, 93-105.‏
Bao, Z., Hu, Q., Qi, W., Tang, Y., Wang, W., Wan, P., Chao, J. & Yang, X.J. (2017) Nitrate reduction in water by aluminum alloys particles. Journal of Environmental Management, 196: 666–673.
Bondonno, C. P., Blekkenhorst, L. C., Liu, A. H., Bondonno, N. P., Ward, N. C., Croft, K. D., & Hodgson, J. M. (2018). Vegetable-derived bioactive nitrate and cardiovascular health. Molecular Aspects of Medicine, 61, 83-91.‏
Chen, Z., Zhang, Z., Qu, C., Pan, D., & Chen, L. (2012). Highly sensitive label-free colorimetric sensing of nitrite based on etching of gold nanorods. Analyst, 137(22), 5197-5200.
Chiu, Y. T., Lin, C. H., Lee, J., & Lin, K. Y. A. (2020). Reduction of nitrate to nitrite in water by acid-washed zero-valent zinc. Separation Science and Technology, 55(4), 761-770.‏
Cortas, N. K., & Wakid, N. W. (1990). Determination of inorganic nitrate in serum and urine by a kinetic cadmium-reduction method. Clinical Chemistry, 36(8), 1440-1443.‏
 Daniel, W. L., Han, M. S., Lee, J. S., & Mirkin, C. A. (2009). Colorimetric nitrite and nitrate detection with gold nanoparticle probes and kinetic end points. Journal of the American Chemical Society, 131(18), 6362-6363.
Greer, F. R., Shannon, M., Committee on Nutrition, & Committee on Environmental Health. (2005). Infant methemoglobinemia: the role of dietary nitrate in food and water. Pediatrics, 116(3), 784-786.‏
‏Honikel, K. O. (2008). The use and control of nitrate and nitrite for the processing of meat products. Meat Science, 78(1-2), 68-76.‏
Hooda, V., Sachdeva, V., & Chauhan, N. (2016). Nitrate quantification: recent insights into enzyme-based methods. Reviews in Analytical Chemistry, 35(3), 99-114.‏
Hord, N. G., Tang, Y., & Bryan, N. S. (2009). Food sources of nitrates and nitrites: the physiologic context for potential health benefits. The American Journal of Clinical Nutrition, 90(1), 1-10.‏
Hyde, E. R., Andrade, F., Vaksman, Z., Parthasarathy, K., Jiang, H., Parthasarathy, D. K., & Bryan, N. S. (2014). Metagenomic analysis of nitrate-reducing bacteria in the oral cavity: implications for nitric oxide homeostasis. PLoS One, 9(3), e88645.‏
Kelly, K.L., Coronado, E., Zhao, L. L., & Schatz, G. C. (2003). The optical properties of metal nanoparticles: the influence of size , shape and dielectric environment. The Journal of Physical Chemistry B, 107(3), 668-677.
Kumar, M., & Chakraborty, S. (2006). Chemical denitrification of water by zero-valent magnesium powder. Journal of Hazardous Materials, 135(1-3), 112-121.‏
Kumar, V. V., & Anthony, S. P. (2014). Highly selective silver nanoparticles based label free colorimetric sensor for nitrite anions. Analytica Chimica Acta, 842, 57-62.
Lundberg, J. O., Feelisch, M., Björne, H., Jansson, E. Å., & Weitzberg, E. (2006). Cardioprotective effects of vegetables: is nitrate the answer? Nitric Oxide, 15(4), 359-362.‏
Manassaram, D. M., Backer, L. C., Messing, R., Fleming, L. E., Luke, B., & Monteilh, C. P. (2010). Nitrates in drinking water and methemoglobin levels in pregnancy: a longitudinal study. Environmental Health, 9(1), 1-12.‏
Michalski, R., & Kurzyca, I. (2006). Determination of Nitrogen Species (Nitrate, Nitrite and Ammonia Ions) in Environmental Samples by Ion Chromatography. Polish Journal of Environmental Studies, 15(1).‏
Mura, S., Greppi, G., Roggero, P. P., Musu, E., Pittalis, D., Carletti, A., ... & Irudayaraj, J. (2015). Functionalized gold nanoparticles for the detection of nitrates in water. International journal of environmental science and technology, 12, 1021-1028.‏
Provin, T., & Hossner, L. R. (2001). What Happens to Nitrogen in Soils? Texas FARMER Collection.‏
Sachdeva, V., & Hooda, V. (2014). A new immobilization and sensing platform for nitrate quantification. Talanta, 124, 52-59.‏
Salomez, J., & Hofman, G. (2002). Nitrate extraction from fresh plant material by means of a methanol: water extraction solution. Communications in soil science and plant analysis, 33(15-18), 3397-3404.‏
Santamaria, P. (2006). Nitrate in vegetables: toxicity, content, intake and EC regulation. Journal of the Science of Food and Agriculture, 86(1), 10-17.‏
Sorte, K., & Basak, A. (2010). Development of a modified copper-cadmium reduction method for rapid assay of total nitric oxide. Analytical Methods, 2(7), 944-947.
‏Speijers, G. & Van den Brandt, P. (2003). Nitrite and potential endogenous formation of N-nitroso compounds; safety evaluation of certain food additives, JECFA, WHO Food Additives Series, 50, 49-74.
Suzuki, H., Iijima, K., Moriya, A., McElroy, K., Scobie, G., Fyfe, V., & McColl, K. E. L. (2003). Conditions for acid catalysed luminal nitrosation are maximal at the gastric cardia. Gut, 52(8), 1095-1101.‏
Suzuki, T., Moribe, M., Oyama, Y. & Niinae, M. (2012) Mechanism of nitrate reduction by zero-valent iron: equilibrium and kinetics studies. Chemical Engineering Journal, 183: 271–277.
Taiz, L., Zeiger, E., Møller, I. M., & Murphy, A. (2015). Plant physiology and development (No. Ed. 6). Sinauer Associates Incorporated.‏ 
Tannenbaum, S. R., & Walstra, P. (2000). Handbook of Water Analysis, Edit. Nollet LM, M,‏ in Dekker, New York.
Titov, V. Y., & Petrenko, Y. M. (2005). Proposed mechanism of nitrite-induced methemoglobinemia. Biochemistry (Moscow), 70(4), 473-483.‏
Tratnyek, P. G., Salter, A. J., Nurmi, J. T., & Sarathy, V. (2010). Environmental applications of zerovalent metals: iron vs. zinc. In Nanoscale Materials in Chemistry: Environmental Applications (pp. 165-178). American Chemical Society.‏
Uddin, R., Thakur, M. U., Uddin, M. Z., & Islam, G. R. (2021). Study of nitrate levels in fruits and vegetables to assess the potential health risks in Bangladesh. Scientific Reports, 11(1), 1-9.‏
Wang, S., Lin, K., Chen, N., Yuan, D., & Ma, J. (2016). Automated determination of nitrate plus nitrite in aqueous samples with flow injection analysis using vanadium (III) chloride as reductant. Talanta, 146, 744-748.‏
Wang, Q. H., Yu, L. J., Liu, Y., Lin, L., Lu, R. G., Zhu, J. P., & Lu, Z. L. (2017). Methods for the detection and determination of nitrite and nitrate: A review. Talanta, 165, 709-720.‏
Ward, M. H., DeKok, T. M., Levallois, P., Brender, J., Gulis, G., Nolan, B. T., & VanDerslice, J. (2005). Workgroup report: drinking-water nitrate and health—recent findings and research needs. Environmental Health Perspectives, 113(11), 1607-1614.‏
World Health Organization. (2011). Nitrate and nitrite in drinking-water: background document for development of WHO guidelines for drinking-water quality, No. WHO/SDE/WSH/07.01/16
World Health Organization. (2016). Nitrate and nitrite in drinking-water.
 Zhang, J., Yang, C., Wang, X., & Yang, X. (2012). Colorimetric recognition and sensing of nitrite with unmodified gold nanoparticles based on a specific diazo reaction with phenylenediamine. Analyst, 137(14), 3286-3292.‏